Herbicidal heterocyclicbenzylsulfonamides

ABSTRACT

Novel benzylsulfonamide compounds containing ortho-heterocyclic substitutents such as N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-[5-(methylthio-1,3,4-oxadiazol-2-yl]benzenemethanesulfonamide are useful as preemergent and/or postemergent herbicides or plant growth regulants.

RELATED APPLICATIONS

This is a division of application Ser. No. 07/069,236, filed July 2,1987, now abandoned, which is a continuation-in-part of my copendingapplication U.S. Ser. No. 618,731 filed June 8, 1984, now abandoned.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 4,420,325, issued Dec. 13, 1983, discloses herbicidalbenzylsulfonamides of formula ##STR1## where R₁ is F, Cl, Br, CF₃, C₁-C₃ alkoxy, C₁ -C₃ alkyl, NO₂, CO₂ R₄, SO₂ R₅, SO₂ NR₆ R₇, SO₂N(OCH₃)CH₃, SO₂ OCH₂ CF₃, OSO₂ R₅ or CH₂ L.

European Patent Applications (EP-A) 83,975, published July 20, 1983 and85,476, published Aug. 10, 1983, disclose herbicidal compounds offormula ##STR2## where Q is various 5- and 6-membered unsaturated,saturated and partially saturated heterocycles.

U.S. Pat. No. 4,370,480, issued Jan. 25, 1983, discloses herbicidalsulfonamides of formula ##STR3## where R₁ may be ##STR4## and B is O orS(O)_(G).

SUMMARY OF THE INVENTION

This invention relates to novel compounds of Formula I, suitableagricultural compositions containing them and their method-of-use asgeneral and/or selective preemergence and/or postemergence herbicidesand/or plant growth regulants. ##STR5## wherein

R is H, F, Cl, Br, CH₃, CF₃, OCH₃, OCHF₂ SCH₃ or SCHF₂ ;

Q is a saturated, 5- or 6-membered ring containing 1 to 2 heteroatomsselected from 0-2 S or 0-2 O or an unsaturated 5- or 6-membered ringcontaining 1 to 3 heteroatoms selected from 0-1 S, 0-1 O or 0-3 N and Qmay optionally be substituted by one or more groups selected from C₁ -C₄alkyl, halogen, C₁ -C₃ alkoxy, mercapto, C₁ -C₃ alkylthio, C₁ -C₂haloalkoxy, C₃ -C₄ alkenylthio, C₁ -C₂ haloalkylthio or SCH₂ CN;

A is ##STR6##

X is CH₃, OCH₃, OCH₂ CH₃, Cl, F, Br, I, OCF₂ H, CH₂ F, OCH₂ CH₂ F, OCH₂CHF₂, OCH₂ CF₃ or CF₃ ;

Y is H, CH₃, OCH₃, OC₂ H₅, CH₂ OCH₃, NHCH₃, N(OCH₃)CH₃, C₂ H₅, N(CH₃)₂,CF₃, SCH₃, OCH₂ CH═CH₂, OCH₂ C.tbd.CH, CH₂ OC₂ H₅, OCH₂ CH₂ OCH₃, CH₂SCH₃, ##STR7## OCF₂ H, SCF₂ H or cyclopropyl;

m is 2 or 3;

L₁ and L₂ are independently O or S;

R₄ is H or CH₃ ;

R₅ and R₆ are independently C₁ -C₂ alkyl;

Z is CH or N;

Y₁ is O or CH₂ ;

X₁ is CH₃, OCH₃, OC₂ H₅ or OCF₂ H; and

Y₂ is H or CH₃ ; provided that

(a) when X is Cl, F, Br or I, then Z is CH and Y is OCH₃, OC₂ H₅,N(OCH₃)CH₃, NHCH₃, N(CH₃)₂ or OCF₂ H;

(b) when Q is a saturated ring containing 2 heteroatoms or anunsaturated ring containing oxygen and sulfur, said heteroatoms are notbonded directly to one another;

(c) when Q is Q-7 and R₁ is SR₃, then X is CH₃ or OCH₃, Y is OCH₃ and Zis CH or N; and

(d) when X or Y is OCF₂ H, then Z is CH;

and their agriculturally suitable salts.

Preferred for reasons of greater ease of synthesis and/or greaterherbicidal efficacy are:

(1) Compounds of Formula I where R is H, Q is ##STR8##

R₁ is H, C₃, C₂ H₅, SR₃, OCH₃ or OCH₂ CH₃ ;

R₂ is H or Cl; and

R₃ is H, C₁ -C₄ alkyl, CH₂ CN, CHF₂ or CH₂ CH═CH₂ ;

(2) Compounds of Preferred 1 where A is A-1 and Y is CH₃, OCH₃, CH₂OCH₃, NHCH₃, CH₂ CH₃, CH(OCH₃)₂ or cyclopropyl;

(3) Compounds of Preferred 2 where X is CH₃, OCH₃, Cl, Br or OCF₂ H;

(4) Compounds of Preferred 3 where Q is Q-1, Q-2 or Q-3;

(5) Compounds of Preferred 3 where Q is Q-4, Q-5 or Q-6;

(6) Compounds of Preferred 3 where Q is Q-7, Q-8 or Q-9;

(7) Compounds of Preferred 6 where Q is Q-7;

(8) Compounds of Preferred 3 where Q is Q-10; Q-11, Q-12, Q-13 or Q-14;

(9) Compounds of Preferred 3 where Q is Q-15; Q-16 or Q-17;

(10) Compounds of Preferred 3 where Q is Q-18, Q-19 or Q-20;

(11) Compounds of Preferred 3 where Q is Q-21 or Q-22;

(12) Compounds of Preferred 3 where Q is Q-23;

(13) Compounds of Preferred 3 where Q is Q-24, Q-25, Q-26 or Q-27;

(14) Compounds of Preferred 3 where Q is Q-28, Q-29, Q-30, Q-31, Q-32 orQ-33.

An exemplary compound of the present invention isN-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-[5-(methylthio-1,3,4-oxadiazol-2yl]benzenemethanesulfonamide,m.p. 174°-177° C.

DETAILED DESCRIPTION OF THE INVENTION Synthesis

The compounds of Formula I can be prepared by one or more of the methodsdescribed below in Equations 1, 2 or 3.

As shown in Equation 1 below, the compounds of Formula I can be preparedby treating sulfonamides of Formula II with the methyl ester of apyrimidine or triazinecarbamic acid of Formula III in the presence of anequimolar quantity of trimethylaluminum. ##STR9## wherein Q, R and A areas previously defined.

The reaction of Equation 1 is best carried out at temperatures between23° to 83° C. in an inert solvent such as methylene chloride or1,2-dichloroethane for 12 to 96 hours under an inert atmosphere. Theproduct can be isolated by the addition of an aqueous acetic acidsolution followed by extraction of the product into methylene chlorideor direct filtration of a product of low solubility. The product canordinarily be purified by trituration with solvents such as n-butylchloride or ether or by chromatography procedures. The methylcarbamates, III, can be conveniently prepared by treatment of thecorresponding heterocyclic amines of Formula VI with dimethyl carbonateor methyl chloroformate in the presence of a base such as sodium hydrideor pyridine.

Further details of this reaction and the preparation of the carbamatesof Formula III can be found in EP-A No. 83,975 (published July 20,1983).

Alteratively, compounds of Formula I can be prepared by the reaction ofsulfonamides of Formula II with the phenyl ester of the appropriatecarbamic acid, IV, in the presence of an equimolar quantity of atertiary amine base such as 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).##STR10## wherein A is as previously defined.

The reaction of Equation 2 is best carried out at 20° to 30° C. in aninert solvent such as dioxane or acetonitrile. Aqueous acid work-upaffords the desired products, according to the teachings of EP-A No.70,804 (published Jan. 26, 1983) and South African Patent ApplicationNos. 825,042 and 830,441. The phenyl carbamates, IV, can be synthesizedby treating the corresponding heterocyclic amines of Formula VI withdiphenyl carbonate or phenyl chloroformate in the presence of a basesuch as sodium hydride or pyridine.

Also, many components of Formula I can be prepared by reacting anappropriate sulfonyl isocyanate, V, with the appropriately substitutedaminoheterocycle, VI, as shown in Equation 3 below, ##STR11## wherein Rand A are as previously defined; and Q is Q-1 to Q-22 and Q-24 to Q-27.

The reaction is best performed in an inert solvent such as methylenechloride, tetrahydrofuran, acetonitrile or toluene at 23° to 100° C. for1 to 24 hours. In cases where the products are insoluble in the reactionsolvent, they may be isolated by simple filtration. When the productsare soluble, they may be isolated by evaporation of the solvent andtrituration of the residue with an appropriate solvent such as1-chlorobutane, diethyl ester, methanol or ethyl acetate and filtration.

Sulfonyl isocyanates of Formula V above may be prepared, although oftentimes in low yields, from corresponding sulfonamides of Formula II bymethods analogous to those described in U.S. Pat. Nos. 4,238,621,4,420,325 (issued Dec. 13, 1983) and EP-A No. 83,975 (published July 20,1983). By a preferred method, sulfonamides are reacted with phosgene, inthe presence of n-butyl isocyanate and a tertiary amine catalyst, atreflux in an inert solvent such as xylenes. A preferred catalyst is1,4-diazabicyclooctane-[2.2.2]octane (DABCO). Alternatively,isocyanates, V, may be prepared by (1) reacting sulfonamides, II, withn-butyl isocyanate and a base such as potassium carbonate at reflux inan inert solvent such as 2-butanone to form a n-butyl sulfonylurea; and(2) reacting this compound with phosgene and DABCO catalyst at reflux inxylenes solvent.

Benzenemethanesulfonamides of Formula II can be prepared fromappropriately substituted benzyl chlorides or benzyl bromides of FormulaVII by a sequence of reactions described in Equation 4 below. ##STR12##wherein M is chlorine or bromine; R is as originally defined; except Ris not SCH₃ or SCF₂ H; Q is Q-1 to Q-20, and Q-23.

Reaction 4(a)

The conversion of alkyl halides to isothiouronium salts is wellprecedented in the literature. For relevant examples, see T. B. Johnsonand J. M. Sprague, J. Am. Chem. Soc., 58, 1348 (1936); 59, 1837 and 2439(1937); 61, 176 (1939). In a typical procedure, a benzyl halide ofFormula VII is treated with thiourea in a suitable solvent such asethanol or tetrahydrofuran. Temperatures of 40°-80° C. over one-half to4 hours are typically required to complete the reaction. The productsalts, VIII, are isolated by cooling and filtration or by concentrationto remove the solvent. The salts, VIII, are generally sufficiently pureto be carried on directly to step 4(b) without further purification.

Reaction 4(b)

The oxidative chlorination of isothiouronium salts to afford sulfonylchlorides is most conveniently effected according to the procedure ofJohnson as described in J. Am. Chem. Soc., 61, 2548 (1939). Thus, theappropriate isothiouronium salts, VIII, are suspended in aqueous aceticacid and treated with at least three equivalents of chlorine attemperatures between 0° and 20° C. The product sulfonyl chlorides ofFormula IX are isolated by filtration or extraction into methylenechloride followed by drying and evaporation of the solvent. No furtherpurification of the sulfonyl chlorides is generally necessary.

Reaction 4(c)

The conversion of sulfonyl chlorides to sulfonamides is well precedentedin the literature. For example, exposure of a sulfonyl chloride toammonium hydroxide results in the formation of the correspondingsulfonamide, e.g., Crossley et al., J. Am. Chem. Soc., 60, 2223 (1938).Also, sulfonyl chlorides IX can be suspended in an aprotic solvent suchas diethyl ether, 1-chlorobutane, methylene chloride, or tetrahydrofuranand contacted with an excess of anhydrous ammonia at a temperature ofabout -20° to 25° C. The product sulfonamides, II, are isolated byfiltration and washing with water to remove the by-product ammoniumchloride, and concentrating the organic solution. The crudesulfonamides, II, can be purified by recrystallization or chromatographyprocedures.

Alternatively, sulfonamides of Formula II may be prepared from theappropriate benzyl halides of Formula VII by a three-step sequence ofreactions shown below in Equation 5. ##STR13## wherein R and Q are aspreviously defined.

Reaction 5(a)

The displacement reactions are best carried out by treating the benzylhalides, VII, with excess sodium thiosulfate (generally about 10 to 30%mole excess) at about 40° to 90° C. for one to 24 hours in an aqueousN,N-dimethylformamide (DMF) solvent. Preferably, sufficient water isused to insure solubility of the sodium thiosulfate. After the reactionis complete, the suspension is cooled and added to excess water. Afterwashing the aqueous suspension with methylene chloride to removeinsoluble impurities, the aqueous solution, containing thiosulfate salt,X, is reacted directly as shown in Equation 5(b) without isolation of X.

Reaction 5(b)

The oxidative chlorination of thiosulfate salt, X, is most convenientlyeffected by addition of methylene chloride solvent to the aqueoussolution of Equation 5(a) and treating the suspension with excesschlorine (at least three equivalents, preferably three to fiveequivalents) at temperatures between 0° to 20° C. The reaction generallyrequires about 0.5 to 5 hours at 0° to 20° C. After completion ofreaction, crude sulfonyl chlorides, IX, are isolated by separation,drying and evaporation of the methylene chloride layers.

Reaction 5(c)

The amination reaction of Equation 5(c) is carried out as describedabove for Equation 4(c).

Also, certain sulfonamides of Formula II may be prepared fromappropriately substituted o-(methoxycarbonyl)benzenemethanesulfonamides,VII, as shown in Equation 6 below. ##STR14## wherein M' is Cl, Br or I;and R and R₃ are as previously defined.

Reaction 6(a)

The conversion of carboxylic esters to hydrazides is well known in theliterature. In a typical procedure, a carboxylic ester of Formula XI isreacted with an excess of hydrazine monohydrate (about 10 to 30% moleexcess) in an inert solvent such as methanol or ethanol at reflux forone to 24 hours. The hydrazide products, XII, are isolated by coolingand filtration or by concentration to remove the solvent and trituratingthe hydrazide residue, XII, with water. The hydrazides, XII, aregenerally sufficiently pure to be carried on directly to step 6(b), butmay be purified further by recrystallization procedures. Esters of thegeneral Formula XI are known; see U.S. Pat. No. 4,420,325.

Reaction 6(b)

The conversion of hydrazides to 2-mercaptooxidiazoles is also well knownin the literature, e.g., R. W. Young and K. H. Wood, J. Am. Chem. Soc.,77, 400 (1955). In a typical procedure, hydrazides, XII, are heatedunder reflux with equimolar amounts of potassium hydroxide and an excessof carbon disulfide in methanol or ethanol solvent until the evolutionof hydrogen sulfide has nearly stopped. Oxadiazoles, XIII, are isolatedby concentration of the solvent, addition of water to the residue,filtration of the aqueous suspension to remove insoluble impurities,acidification with hydrochloric acid of the aqueous filtrate andfiltration. Oxadiazoles, XIII, are generally pure enough to carry on tostep 6(c), but may be further purified by recrystallization procedures.

Reaction 6(c)

Alkylation of 2-mercaptooxidazoles is also well known in the literature,e.g. S. Girl et al., Agr. Biol. Chem., 40, 17 (1976). Typically,oxidazoles, XIII, are reacted with an equimolar amount of a base such aspotassium hydroxide and excess alkylating agent, R₃ --M', at refluxtemperatures in an inert solvent such as methanol or ethanol for 0.5 to24 hours. Sulfonamides, IIa, are isolated by concentration of thesolvent, addition of water to the residue and filtration. For the casewhere R₃ ═CF₂ H, the reaction is preferably run in DMF solvent at60°-90° C. with excess potassium carbonate as base. Products IIa,isolated by addition of water and filtration, may be further purified byrecrystallization procedures.

Benzyl halides of Formula VII, where Q is Q-1 to Q-20 and Q-23, may beprepared as shown below in Equation 7 by treatment of the appropriatelysubstituted toluene derivatives, XIV, with either N-bromosuccinimide(NBS) or N-chlorosuccinimide (NCS). ##STR15## where R is as previouslydefined; and Q is Q-1 to Q-20 and Q-23.

The reactions of Equation 7 can be most conveniently carried out byheating a solution of the toluene derivatives, XIV, and eitherN-bromosuccinimide or N-chlorosuccinimide in a suitable solvent such ascarbon tetrachloride at reflux temperature. A free radical catalyst suchas azoisobutyronitrile or benzoyl peroxide is usually employed toinitiate the reaction. When the reaction is complete, the cooledsolution is filtered to remove the by-product succinimide and thefiltrate concentrated in vacuo. The benzyl halides of Formula VIIa andVIIb are often obtained in a sufficiently pure state for furthertransformation. They may, however, be further purified byrecrystallization or chromatography procedures obvious to those skilledin the art.

Benzyl halides of Formula VII containing an o-furan or thiophene group(Q is Q-24 to Q-27) may be prepared by the sequence of reactions shownbelow in Equation 8. ##STR16## wherein R is H; W is O or S; and Q isQ-24 to Q-27.

Equation (8a,b)

A N,N-dimethylbenzylamine of Formula XV is dissolved in an ethanolsolvent, such as tetrahydrofuran, and one equivalent or n-butyllithiumin hexane is added at 0°-25° C. After 1-5 hours at 0°-25°, the compoundof Formula XVI is formed. This is not isolated, but one equivalent of acopper(I) iodide salt is added at -20° to 0°, followed by 1-1.5equivalents of an appropriate iodofuran or iodothiophene of FormulaXVII. The reaction mixture is then heated at 40°-70° C. for 1-3 days,concentrated, poured onto aqueous ammonia, extracted with methylenechloride, dried and concentrated to provide compounds of Formula XVIII.The compounds are further purified by chromatography procedures obviousto one skilled in the art.

Equation 8(c)

The compounds of Formula XVIII are treated with cyanogen bromide in anethereal solvent, such as tetrahydrofuran, and stirred at 20°-70° C. forone to 24 hours to provide benzyl bromides of Formula VIIc, according toteachings of Org. React., 7, 198 (1953) and Ber., 43, 3209 (1910). Thecompounds are isolated by concentration in vacuo and purified bychromatography procedures.

Alternatively, benzyl halides of Formula VIIc above may be prepared bythe sequence of reactions shown below in Equation 9. ##STR17## wherein Ris as originally defined; and W is O or S.

Reaction 9(a)

In this reaction a furyl- or thienylcopper compound of Formula XX isreacted with an appropriate N,N-dimethyl-o-iodobenzylamine of FormulaXIX in a solvent such as pyridine or quinoline. The copper compounds ofFormula XX are prepared by reacting the corresponding lithium compoundswith cuprous iodide or cuprous bromide in a solvent such as diethylether. The detailed procedures for analogous types of reactions aredescribed in the following references: M. Nilsson and C. Ullenius, Acta.Chem. Scand., 24, 2379-2388 (1970); C. Ullenius, Acta. Chem. Scand., 26,3383-3386 (1972).

Reaction 9(b)

This reaction is run similar to that described in Equation 8(c).

Benzyl halides of Formula VII containing a tetrahydrofuran group (Q isQ-21 or Q-22) may be prepared by the sequence of reactions shown belowin Equation 10. ##STR18## wherein R is as originally defined.

Reaction 10(a)

Reductions of furans to tetrahydrofurans are will known in theliterature. The choice of catalyst, solvent, pressure and temperaturefor such reductions has been reviewed by Samuel Sevadash in The Furansby A. P. Dunlop and F. N. Peters, Reinhold Publishing Corporation, NewYork, N.Y., 1953, pp. 674-713; and by P. N. Rylander in CatalyticHydrogenation in Organic Synthesis, Academic Press, 1979, pp. 227-234.

The o-heterocyclic toluenes of Formula XIV above are importantintermediates for the preparation of many of the compounds of thisinvention. They can be prepared by those skilled in the art by theapplication of appropriate methods selected from the variety of knownliterature procedures for preparing substituted aromatic heterocycles.

For instance, as illustrated in equation 11(a) below, EP-A No. 83,975(published July 20, 1983), and references cited therein, teach methodsfor transforming various o-(substituted)nitrobenzenes of Formula XXII too-(heterocyclic)nitrobenzenes of Formula XXIII, where Q is Q-1 to Q-20.As illustrated in Equation 11(b) below, by substituting similarlysubstituted o-(substituted)toluenes of Formula XXIV for nitrobenzenes,XXII, and carrying out the appropriate reactions taught in EP-A No.83,975, or simple modifications thereof, those skilled in the art canprepare compounds of Formula XIVa, where Q is Q-1 to Q-20. ##STR19##wherein R is as originally defined; Q is Q-1 to Q-20; and J is anappropriate functional group taught in EP-A No. 83,975, and referencescited therein, to prepare ortho-groups Q-1 to Q-20.

In addition, o-(pyrimidin-2-yl)toluenes of Formula XIVb, where Q isQ-23, are prepared from amidine salts, XXV, as shown in Equation 12.##STR20## wherein R and Q-23 are as previously defined.

The reaction of Equation 12 is accomplished by heating salts, XXV, with1,1,3,3-tetraethoxy (or methoxy)propane in an inert solvent such ethanolat 25°-80° C. for about 1 to 10 hours. The products, XIVb, are isolatedby addition of water, extraction with methylene chloride, drying andconcentration of the filtrate.

The sulfonamides of Formula II, substituted by an o-cyclic-acetal orthioacetal group (Q is Q-28 to Q-33), may be prepared by known methodsobvious to those skilled in the art.

The heterocyclic amine intermediates such as those depicted by FormulaVI above in Equation 3 can be prepared by methods known in theliterature, or simple modifications thereof, by those skilled in theart. For instance, the synthesis of aminopyrimidines and triazines hasbeen reviewed in "The Chemistry of Heterocyclic Compounds", a seriespublished by Interscience Publishers, Inc., New York and London.Aminopyrimidines are also described by D. J. Brown in the "Pyrimidines",Vol. 16 of this series. Aminotriazines are also reviewed by E. M. Smolinand L. Rapaport in "s-Triazines and Derivatives", Vol. 13 of the sameseries. The synthesis of triazines is also described by F. C. SchaeferU.S. Pat. No. 3,154,547 and by K. R. Huffman and F. C. Schaefer, J. Org.Chem., 28, 1812 (1963).

The 5,6-dihydrofuropyrimidin-2-amines, the cyclopentapyrimidin-2-amines(VI, A is A-2) and the 6,7-dihydro-5H-pyranopyrimidin-2-amines (VI, A isA-3) are prepared as described in EP-A No. 15,683. Synthesis of thefuropyrimidin-2-amines (VI. A is A-4) are described in EP-A No. 46,677,Pyrimidine and triazine amines in which Y is such groups asdialkoxymethyl of 1,3-dioxolan-2-yl are prepared as described in EP-ANo. 84,224 (published July 27, 1983). Also, South African PatentApplication No. 837,434 (published Oct. 5, 1983) describes methods forthe synthesis of cyclopropylpyrimidines and triazine amines substitutedby such groups as halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, amino,alkylamino, dialkylamino or alkoxyalkyl. Also, South African PatentApplication Nos. 825,045, and 825,671 describe methods for the synthesisof aminopyrimidines and triazines substituted by such groups ashaloalkoxy or haloalkylthio, e.g., OCH₂ CH₂ Cl, OCH₂ CF₃ or SCF₂ H.

Agriculturally suitable salts of compounds of Formula I are also usefulherbicides and can be prepared in a number of ways known to the art. Forexample, metal salts can be made by contacting compounds of Formula Iwith a solution of an alkali or alkaline earth metal salt having asufficiently basic anion (e.g., hydroxide, alkoxide, carbonate orhydroxide). Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of onecation for another.

Cationic exchange can be effected by direct contact of an aqueoussolution of a salt of a compound of Formula I (e.g., alkali orquaternary amine salt) with a solution containing the cation to beexchanged. This method is most effective when the desired saltcontaining the exchanged cation is insoluble in water and can beseparated by filtration.

Exchange may also be effected by passing an aqueous solution of a saltof a compound of Formula I (e.g., an alkali metal or quaternary aminesalt) through a column packed with a cation exchange resin containingthe cation to be exchanged for that of the original salt and the desiredproduct is eluted from the column. This method is particularly usefulwhen the desired salt is water-soluble, e.g., a potassium, sodium orcalcium salt.

Acid addition salts, useful in this invention, can be obtained byreacting a compound of Formula I with a suitable acid, e.g.,p-toluenesulfonic acid, trichloroacetic acid or the like.

The preparation of the compound of this invention is further illustratedby the following specific examples. Unless otherwise indicated,temperatures are in degrees centigrade.

EXAMPLE 1 2-[(Aminosulfonyl)methyl]benzoic acid hydrazide

To a suspension of 84 g of methyl 2-[(aminosulfonyl)methyl]benzoate in300 ml of absolute ethanol was added dropwise 22 g of hydrazinemonohydrate. The thick suspension was heated at reflux for about 16hours to yield a solution, then a thick suspension, at refluxtemperature. The suspension was cooled to 20° C., filtered, and theresidue was washed 1×100 ml of water and suction dried about three hoursto provide 49 g of the subject compound; m.p. 221°-222° C.

Anal. calc. for C₈ H₁₁ N₃ O₃ S: C,41.9; H,4.8; N,18.3; Found: C,42.5;H,4.8; N,18.5.

EXAMPLE 2 2-(5-Mercapto-1,3,4-oxidazol-2-yl)benzenemethanesulfonamide

To a suspension of 11.5 g of the hydrazide prepared in Example 1 in 100ml of absolute ethanol was added a solution of 2.8 g of potassiumhydroxide in 20 ml of water. After stirring several minutes, 4.8 g ofcarbon disulfide was added in one portion. The suspension was refluxed4.5 hours then concentrated in vacuo. After water (about 100 ml) wasadded to the residue and the suspension stirred several minutes, thesuspension was filtered and the filtrate was acidified with concentratedhydrochloric acid (red to litmus paper). The mixture was filtered andthe residue was washed sequentially with 1×25 ml water, 1×10 ml2-propanol and 1×10 ml ethyl ether. The suction-dried residue wasrecrystallized from methanol to give 3 g of the subject compound; m.p.224°-227° C.

Anal. calc. for C₉ H₉ N₃ O₃ S₂ : C,39.8; H,3.4; N,15.5; Found: C,39.4;H,3.4; N,15.4.

EXAMPLE 32-[5-(Methylthio)-1,3,4-oxadiazol-2-yl]benzenemethanesulfonamide

To a solution containing 0.62 g of potassium hydroxide in 50 ml ofmethanol was added 3 g of the oxadiazole prepared in Example 2. Afterstirring about five minutes, 2 g of methyl iodide was added. Thesuspension was refluxed 0.5 hour, cooled to 30° C., an extra 10 g ofmethyl iodide was added, and the suspension was refluxed an additionaltwo hours, then concentrated in vacuo. After water was added to theresidue, the suspension was filtered and the solid was washed with 1×50ml of water. The suction-dried solid was recrystallized from 2-propanolto give 2 g of the subject compound; m.p. 138°-140° C.

Anal. calc. for C₁₀ H₁₁ N₃ O₃ S₂ : C,42.1; H,3.9; N,14.7; Found; C,42.3;H,3.9; N,14.6;

EXAMPLE 4N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-[5-(methylthio)1,3,4-oxadiazol-2-yl]benzenemethanesulfonamide

To a solution containing 0.62 g of the sulfonamide prepared in Example 3contained in 10 ml of p-dioxane was added 0.6 g of phenyl(4.6-dimethoxypyrimidin-2-yl)carbamate followed by dropwise addition of 0.33 g of1,5-diazbicyclo[5.4.0]undec-5-ene (DBU). The solution was stirred atroom temperature for two hours then diluted with about 100 ml of water.The clear solution was acidified with concentrated hydrochloric acid(red to litmus paper), to give a viscous oil. The oil was triturated bydecanting off the aqueous solvent and stirring the oil residue in about5 ml of acetonitrile. After filtering the suspension, the solid residuewas washed with 1×5 ml of warm ethyl acetate to give 0.26 g of thesubject compound; m.p. 174°-177° C.

Anal, calc. for C₁₇ H₁₈ N₆ O₆ S₂ : C,43.8; H,3.9; N,18.0; Found: C,43.5;H,3.9; N,18.1.

NMR (CDCl₃, DMSO-d₆) ppm: δ2.8 (s, 3H, SCH₃); 3.75 (s, 6H, OCH₃); 5.5(s, 2H, CH₂); 5.7 (s, 1H, pyrimidin); 7.4-8.1 (m, 4H; arom.); and 9.7(s, 1H, NH).

IR (nujol): 1680 cm⁻¹ (C═O).

EXAMPLE 5N-[(4-Methoxy-6-methyl1,3,5-triazin-2-yl)aminocarbonyl]-2-[5-methylthio)-1,3,4-oxadiazol-2-benzenemethanesulfonamide

By the procedure of Example 4, 0.62 g of the sulfonamide of Example 3was reacted with 0.57 g of phenyl(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamate and 0.33 g of DBU in 10ml of p-dioxane. After stirring two hours at room temperature thesolution was diluted with about 75 ml of water and acidified withconcentrated hydrochloric acid (red to litmus). Followed filtration, theresidue was washed with 1×5 ml of warm ethyl acetate to give 0.28 g ofthe subject compound; m.p. 175°-177° C.

IR (nujol): 1730 cm⁻¹ (C═O).

NMR (CDCl₁₃) ppm: δ2.6 (s, 3H, OCH₃); 2.8 (s, 3H, SCH₃); 4.0 (s, 3H,CH₃); 5.6 (s, 2H, CH₂); and 7.5-8.0 (m, arom. and NH).

EXAMPLE 6N-(Butylaminocarbonyl)-2[5-(methylthio)-1,3,4-oxadiazol-2-yl]benzenemethanesulfonamide

A suspension containing 16 g of the sulfonamide of Example 3, 7.7 g ofpotassium carbonate and 6.7 g of n-butylisocyanate in 130 of 2-butanonewas refluxed for 4 hours, then stirred overnight at room temperature.After concentrating the mixture in vacuo, the residue was diluted withabout 150 ml of water and the solution was washed 1×100 ml of ethylether. The aqueous layer was acidified with concentrated hydrochloricacid (red to litmus paper) and the resulting suspension was filtered,the suction-dried overnight to give 20 g of the subject compound; m.p.156°-159° C. IR (nujol): 1680 cm⁻¹ (C═O).

EXAMPLE 7 2-[5-(Methylthio)-1,3,4-oxadiazol2-yl]benzenemethanesulfonylisocyanate

A suspension of 18.4 g of compound prepared in Example 6 in 180 ml ofxylene containing 0.8 g DABCO was heated at 130°-135° C. while 3.9 ml ofphosgene was added portionwise at a rate to maintain a refluxtemperature of 130°-135° C. The mixture was refluxed for an additional 2hours, cooled under nitrogen to room temperature, filtered, and thefiltrate was concentrated to dryness in vacuo. A sample of the crudeoily product displayed a characteristic sulfonyl isocyanate band in theIR at 2200 cm⁻¹.

EXAMPLE 8N-[(4-Methyl-6-methoxypyrimidin-2-yl)aminocarbonyl]-2-[5-(methylthio)-1,3,4-oxadiazol-2-yl]benzenemethanesulfonamide

To a suspension of 0.33 g of 2-amino-4-methyl-6-methoxypyrimidine in 10ml of acetonitrile was added 1 g of crude sulfonyl isocyanate preparedin Example 7. The suspension was stirred at room temperature overnight,then filtered, the residue was washed with 25 ml of ethyl ether andsuction dried to give 0.7 g of the subject compound; m.p. 194°-196° C.

NMR(CDCl₃, DMSO): ppm δ2.3 (s, 3H, CH₃) 2.8 (s, 3H, SCH₃); 3.8 (s, 3H,OCH₃); 5.6 (s, 2H, CH₂); 6.3 (s, 1H, pyrimidin); 7.4-7.9 (m, 4H, arom.).

IR (nujol): 1710 cm⁻¹ (C═O).

Using the techniques described in Equations 1-12 and Examples 4, 5, and8, or simple modification thereof, the following compounds in Tables I-Vcan be made by one skilled in the art.

                                      TABLE I                                     __________________________________________________________________________     ##STR21##                                                                    Q              R      X        Y          m.p. °C.                     __________________________________________________________________________    Q-1            H      CH.sub.3 CH.sub.3                                       Q-1            H      OCH.sub.3                                                                              OCH.sub.3                                      Q-1            H      CH.sub.3 OCH.sub.3                                      Q-1            H      Cl       OCH.sub.3                                      Q-1            H      Br       OCH.sub.3                                      Q-2            H      CH.sub.3 CH.sub.3                                       Q-2            H      OCH.sub.3                                                                              OCH.sub.3                                      Q-2            H      CH.sub.3 OCH.sub.3                                      Q-2            H      Cl       OCH.sub.3                                      Q-2            H      Br       OCH.sub.3                                      Q-3            H      CH.sub.3 CH.sub.3                                       Q-3            H      OCH.sub.3                                                                              OCH.sub.3                                      Q-3            H      CH.sub.3 OCH.sub.3                                      Q-3            H      Cl       OCH.sub.3                                      Q-4            H      CH.sub.3 CH.sub.3                                       Q-4            H      CH.sub.3 OCH.sub.3                                      Q-4            H      OCH.sub.3                                                                              OCH.sub.3                                      Q-4            H      Cl       OCH.sub.3                                      Q-5            H      CH.sub. 3                                                                              CH.sub.3                                       Q-5            H      OCH.sub.3                                                                              OCH.sub.3                                      Q-5            H      CH.sub.3 OCH.sub.3                                      Q-5            H      Cl       OCH.sub.3                                      Q-6            H      CH.sub.3 CH.sub.3                                       Q-6            H      OCH.sub.3                                                                              OCH.sub.3                                      Q-6            H      CH.sub.3 OCH.sub.3                                      Q-6            H      Cl       OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.3)                                                                    H      OCH.sub.3                                                                              OCH.sub.3  174-177                             Q-7 (R.sub.1 = SCH.sub.3)                                                                    H      CH.sub.3 OCH.sub.3  194-196                             Q-7 (R.sub.1 = SC.sub.2 H.sub.5)                                                             H      OCH.sub.3                                                                              OCH.sub.3  164-167                             Q-7 (R.sub.1 = SC.sub.2 H.sub.5)                                                             H      CH.sub.3 OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.2 CH.sub.2 CH.sub.3)                                                  H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.2 CH.sub.2 CH.sub.3)                                                  H      CH.sub.3 OCH.sub.3                                      Q-7 (R.sub.1 = SCH(CH.sub.3).sub.2)                                                          H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SCH(CH.sub.3).sub.2)                                                          H      CH.sub.3 OCH.sub.3                                      Q-7 (R.sub.1 = S- -n-butyl)                                                                  H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = S-  -n-butyl)                                                                 H      CH.sub.3 OCH.sub.3                                      Q-7 (R.sub.1 = OCH.sub.3)                                                                    H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = OCH.sub.3)                                                                    H      CH.sub.3 OCH.sub.3                                      Q-7 (R.sub.1 = OCH.sub.3)                                                                    H      CH.sub.3 CH.sub.3                                       Q-7 (R.sub.1 = OCH.sub.3)                                                                    H      Cl       OCH.sub.3                                      Q-7 (R.sub.1 = OC.sub.2 H.sub.5)                                                             H      CH.sub.3 OCH.sub.3                                      Q-7 (R.sub.1 = OC.sub.2 H.sub.5)                                                             H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = OC.sub.2 H.sub.5)                                                             H      CH.sub.3 CH.sub.3                                       Q-7 (R.sub.1 = OC.sub.2 H.sub.5)                                                             H      Cl       OCH.sub.3                                      Q-7 (R.sub.1 = H)                                                                            H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = H)                                                                            H      CH.sub.3 OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.2 CN)                                                                 H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.2 CN)                                                                 H      CH.sub.3 OCH.sub.3                                      Q-7 (R.sub.1 = SCF.sub.2 H)                                                                  H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SCF.sub. 2 H)                                                                 H      CH.sub.3 OCH.sub.3                                      Q-8            H      OCH.sub.3                                                                              OCH.sub.3                                      Q-8            H      CH.sub.3 OCH.sub.3                                      Q-8            H      CH.sub.3 CH.sub.3                                       Q-8            H      Cl       OCH.sub.3                                      Q-9            H      OCH.sub.3                                                                              OCH.sub.3                                      Q-9            H      CH.sub.3 OCH.sub.3                                      Q-9            H      CH.sub.3 CH.sub.3                                       Q-9            H      Cl       OCH.sub.3                                      Q-10           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-10           H      CH.sub.3 OCH.sub.3                                      Q-10           H      CH.sub.3 CH.sub.3                                       Q-11 (R.sub.2 = Cl)                                                                          H      OCH.sub.3                                                                              OCH.sub.3                                      Q-11 (R.sub.2 = Cl)                                                                          H      CH.sub.3 OCH.sub.3                                      Q-11 (R.sub.2 = Cl)                                                                          H      Cl       OCH.sub.3                                      Q-11 (R.sub.2 = Cl)                                                                          H      CH.sub.3 CH.sub.3                                       Q-11 (R.sub.2 = H)                                                                           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-11 (R.sub.2 = H)                                                                           H      CH.sub.3 OCH.sub.3                                      Q-12           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-12           H      CH.sub.3 OCH.sub.3                                      Q-13           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-13           H      CH.sub.3 OCH.sub.3                                      Q-13           H      CH.sub.3 CH.sub.3                                       Q-13           H      Cl       OCH.sub.3                                      Q-14           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-14           H      CH.sub.3 OCH.sub.3                                      Q-14           H      CH.sub.3 CH.sub.3                                       Q-14           H      Cl       OCH.sub.3                                      Q-15           H      CH.sub.3 CH.sub.3                                       Q-15           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-15           H      CH.sub.3 OCH.sub.3                                      Q-15           H      Cl       OCH.sub.3                                      Q-16           H      CH.sub.3 CH.sub.3                                       Q-16           H      OCH.sub.3                                                                              CH.sub.3                                       Q-16           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-16           H      CH.sub.3 CH.sub.3                                       Q-16           H      Cl       OCH.sub.3                                      Q-17           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-17           H      CH.sub.3 OCH.sub.3                                      Q-18           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-18           H      CH.sub.3 OCH.sub.3                                      Q-18           H      CH.sub.3 CH.sub.3                                       Q-18           H      Cl       OCH.sub.3                                      Q-19           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-19           H      CH.sub.3 OCH.sub.3                                      Q-20           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-20           H      CH.sub.3 OCH.sub.3                                      Q-21           H      CH.sub.3 CH.sub.3                                       Q-21           H      OCH.sub.3                                                                              CH.sub.3                                       Q-21           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-21           H      Cl       OCH.sub.3                                      Q-22           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-22           H      CH.sub.3 OCH.sub.3                                      Q-23           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-23           H      CH.sub.3 OCH.sub.3                                      Q-23           H      CH.sub.3 CH.sub.3                                       Q-23           H      Cl       OCH.sub.3                                      Q-24           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-24           H      CH.sub.3 OCH.sub.3                                      Q-25           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-25           H      CH.sub.3 OCH.sub.3                                      Q-26           H      CH.sub.3 OCH.sub.3                                      Q-26           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-27           H      OCH.sub.3                                                                              CH.sub.3                                       Q-27           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-1            H      OC.sub.2 H.sub.5                                                                       CH.sub.3                                       Q-1            H      F        OCH.sub.3                                      Q-2            H      I        OCH.sub.3                                      Q-8            H      OCF.sub.2 H                                                                            OCH.sub.3                                      Q-9            H      CH.sub.2 F                                                                             CH.sub.3                                       Q-16           H      OCH.sub.2 CH.sub.2 F                                                                   CH.sub.3                                       Q-7 (R.sub.1 = CH.sub.3)                                                                     H      OCH.sub.2 CHF.sub.2                                                                    CH.sub.3                                       Q-1            H      OCH.sub.2 CF.sub.3                                                                     OCH.sub.3                                      Q-1            H      CF.sub.3 OCH.sub.3                                      Q-1            H      F        OCH.sub.3                                      Q-1            H      OCH.sub.3                                                                              H                                              Q-1            H      Cl       OC.sub.2 H.sub.5                               Q-1            H      OCH.sub.3                                                                              CH.sub.2 OCH.sub.3                             Q-2            H      Cl       NHCH.sub.3                                     Q-3            H      OC.sub.2 H.sub.5                                                                       N(OCH.sub.3)CH.sub.3                           Q-16           H      CH.sub.3 N(CH.sub.3).sub.2                              Q-1            H      OCH.sub.3                                                                              C.sub.2 H.sub.5                                Q-8            H      CF.sub.3 CF.sub.3                                       Q-9            H      CH.sub.3 SCH.sub.3                                      Q-10           H      OCH.sub.3                                                                              OCH.sub.2 CHCH.sub.2                           Q-11 (R.sub.2 = Cl)                                                                          H      CH.sub.3 OCH.sub.2 CCH                                  Q-15           H      OCH.sub.3                                                                              CH.sub.2 OCH.sub.2 CH.sub.3                    Q-1            H      CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3                   Q-2            H      CH.sub.3 CH.sub.2 SCH.sub.3                             Q-1            H      CH.sub.3 CHO                                            Q-18           H      CH.sub.3                                                                                ##STR22##                                     Q-1            H      OCH.sub.3                                                                              CH(OCH.sub.3).sub.2                            Q-8            H      OCH.sub.3                                                                              CH(OC.sub.2 H.sub.5).sub.2                     Q-9            H      OCH.sub.3                                                                              CH(SCH.sub.3).sub.2                            Q-10           H      OCH.sub.3                                                                              C(CH.sub.3)(OCH.sub.3).sub.2                   Q-1            H      OCH.sub.3                                                                               ##STR23##                                     Q-16           H      CH.sub.3                                                                                ##STR24##                                     Q-21           H      OCH.sub.3                                                                               ##STR25##                                     Q-24           H      OCH.sub.3                                                                               ##STR26##                                     Q-23           H      OCH.sub.3                                                                               ##STR27##                                     Q-1            H      OCH.sub.3                                                                               ##STR28##                                     Q-12           H      OCH.sub.3                                                                               ##STR29##                                     Q-17           H      OCH.sub.3                                                                               ##STR30##                                     Q-18           H      Cl       OCF.sub.2 H                                    Q-21           H      CH.sub.3 SCF.sub.2 H                                    Q-1            H      OCH.sub.3                                                                               ##STR31##                                     Q-8            3-F    OCH.sub.3                                                                              OCH.sub.3                                      Q-9            6-Cl   OCH.sub.3                                                                              CH.sub.3                                       Q-1            5-Br   OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SC.sub.2 H.sub.5)                                                             5-CH.sub.3                                                                           OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.3)                                                                    5-CF.sub.3                                                                           OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.3)                                                                    5-OCH.sub.3                                                                          OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.3)                                                                    6-OCF.sub.2 H                                                                        OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.3)                                                                    6-SCF.sub.2 H                                                                        OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.2 CHCH.sub.2)                                                         H      OCH.sub.3                                                                              OCH.sub.3  165-168                             Q-7 (R.sub.1 = SCH.sub.2 CHCH.sub.2)                                                         H      CH.sub.3 OCH.sub.3                                      Q-1            H      CH.sub.3 CH.sub.2 OCH.sub.3                             Q-1            H      OCH.sub.3                                                                              OCF.sub.2 H                                    Q-28           H      CH.sub.3 CH.sub.3                                       Q-28           H      OCH.sub.3                                                                              CH.sub.3                                       Q-28           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-28           H      Cl       OCH.sub.3                                      Q-29           H      CH.sub.3 CH.sub.3                                       Q-29           H      OCH.sub.3                                                                              CH.sub.3                                       Q-29           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-29           H      Cl       OCH.sub.3                                      Q-30           H      CH.sub.3 CH.sub.3                                       Q-30           H      OCH.sub.3                                                                              CH.sub.3                                       Q-30           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-30           H      Cl       OCH.sub.3                                      Q-31           H      CH.sub.3 CH.sub.3                                       Q-31           H      OCH.sub.3                                                                              CH.sub.3                                       Q-31           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-31           H      Cl       OCH.sub.3                                      Q-32           H      CH.sub.3 CH.sub.3                                       Q-32           H      OCH.sub.3                                                                              CH.sub.3                                       Q-32           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-32           H      Cl       OCH.sub.3                                      Q-33           H      CH.sub.3 CH.sub.3                                       Q-33           H      OCH.sub.3                                                                              CH.sub.3                                       Q-33           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-33           H      Cl       OCH.sub.3                                      Q-7 (R.sub.1 = SCH.sub.3)                                                                    5-SCH.sub.3                                                                          OCH.sub.3                                                                              OCH.sub.3                                      Q-1            5-SCH.sub.3                                                                          OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = C.sub.2 H.sub.5)                                                              H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = CH.sub.3)                                                                     H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SH)                                                                           H      OCH.sub.3                                                                              OCH.sub.3                                      Q-7 (R.sub.1 = SH)                                                                           H      CH.sub.3 OCH.sub.3                                      __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________     ##STR32##                                                                    Q             R    X    Y        m.p. °C.                              __________________________________________________________________________    Q-1           H    CH.sub.3                                                                           OCH.sub.3                                             Q-1           H    OCH.sub.3                                                                          OCH.sub.3                                             Q-2           H    CH.sub.3                                                                           OCH.sub.3                                             Q-2           H    OCH.sub.3                                                                          OCH.sub.3                                             Q-3           H    OCH.sub.3                                                                          OCH.sub.3                                             Q-3           H    CH.sub.3                                                                           OCH.sub.3                                             Q-4           H    CH.sub.3                                                                           OCH.sub.3                                             Q-5           H    CH.sub.3                                                                           OCH.sub.3                                             Q-6           H    CH.sub.3                                                                           OCH.sub.3                                             Q-7 (R.sub.1 = SCH.sub.3)                                                                   H    CH.sub.3                                                                           OCH.sub.3                                                                              175-177                                      Q-7 (R.sub.1 = SCH.sub.3)                                                                   H    OCH.sub.3                                                                          OCH.sub.3                                                                              180-185                                      Q-7 (R.sub.1 = SC.sub.2 H.sub.5)                                                            H    OCH.sub.3                                                                          CH.sub.3                                              Q-7 (R.sub.1 = SC.sub.2 H.sub.5)                                                            H    OCH.sub.3                                                                          OCH.sub.3                                             Q-7 (R.sub.1 = SCH.sub.2 CH.sub.2 CH.sub.3)                                                 H    OCH.sub.3                                                                          CH.sub.3                                              Q-7 (R.sub.1 = SCH.sub.2 CH.sub.2 CH.sub.3)                                                 H    OCH.sub.3                                                                          OCH.sub.3                                             Q-7 (R.sub.1 = SCH(CH.sub.3).sub.2)                                                         H    OCH.sub.3                                                                          CH.sub.3                                              Q-7 (R.sub.1 = SCH(CH.sub.3).sub.2)                                                         H    OCH.sub.3                                                                          OCH.sub.3                                             Q-7 (R.sub.1 = S- -n-butyl)                                                                 H    CH.sub.3                                                                           OCH.sub.3                                             Q-7 (R.sub.1 = SCH.sub.2 CN)                                                                H    OCH.sub.3                                                                          CH.sub.3                                              Q-7 (R.sub.1 = SCH.sub.2 CN)                                                                H    OCH.sub.3                                                                          OCH.sub.3                                             Q-7 (R.sub.1 = SCF.sub.2 H)                                                                 H    CH.sub.3                                                                           OCH.sub.3                                             Q-7 (R.sub.1 = SCF.sub.2 H)                                                                 H    OCH.sub.3                                                                          OCH.sub.3                                             Q-7 (R.sub.1 = OCH.sub.3)                                                                   H    CH.sub.3                                                                           OCH.sub.3                                             Q-7 (R.sub.1 = OCH.sub.3)                                                                   H    OCH.sub.3                                                                          OCH.sub.3                                             Q-7 (R.sub.1 = OC.sub.2 H.sub.5)                                                            H    OCH.sub.3                                                                          CH.sub.3                                              Q-7 (R.sub.1 = H)                                                                           H    CH.sub.3                                                                           OCH.sub.3                                             Q-7 (R.sub.1 = H)                                                                           H    OCH.sub.3                                                                          OCH.sub.3                                             Q-8           H    CH.sub.3                                                                           OCH.sub.3                                             Q-8           H    OCH.sub.3                                                                          OCH.sub.3                                             Q-9           H    OCH.sub.3                                                                          CH.sub.3                                              Q-9           H    OCH.sub.3                                                                          OCH.sub.3                                             Q-10          H    CH.sub.3                                                                           OCH.sub.3                                             Q-11 (R.sub.2 = Cl)                                                                         H    CH.sub.3                                                                           OCH.sub.3                                             Q-11 (R.sub.2 = H)                                                                          H    CH.sub.3                                                                           OCH.sub.3                                             Q-12          H    CH.sub.3                                                                           OCH.sub.3                                             Q-13          H    CH.sub.3                                                                           OCH.sub.3                                             Q-13          H    OCH.sub.3                                                                          OCH.sub.3                                             Q-14          H    CH.sub.3                                                                           OCH.sub.3                                             Q-15          H    CH.sub.3                                                                           OCH.sub.3                                             Q-16          H    OCH.sub.3                                                                          OCH.sub.3                                             Q-16          H    CH.sub.3                                                                           OCH.sub.3                                             Q-17          H    CH.sub.3                                                                           OCH.sub.3                                             Q-18          H    CH.sub.3                                                                           OCH.sub.3                                             Q-19          H    CH.sub.3                                                                           OCH.sub.3                                             Q-20          H    CH.sub.3                                                                           OCH.sub.3                                             Q-21          H    CH.sub.3                                                                           OCH.sub.3                                             Q-22          H    CH.sub.3                                                                           OCH.sub.3                                             Q-23          H    CH.sub.3                                                                           OCH.sub.3                                             Q-23          H    OCH.sub.3                                                                          OCH.sub.3                                             Q-24          H    CH.sub.3                                                                           OCH.sub.3                                             Q-25          H    CH.sub.3                                                                           OCH.sub.3                                             Q-26          H    CH.sub.3                                                                           OCH.sub.3                                             Q-27          H    CH.sub.3                                                                           OCH.sub.3                                             Q-8           3-F  OCH.sub.3                                                                          CH.sub.3                                              Q-9           6-Cl OCH.sub.3                                                                          CH.sub.3                                              Q-1           5-Br CH.sub.3                                                                           OCH.sub.3                                             Q-7 (R.sub.1 = SC.sub.2 H.sub.5)                                                            5-CH.sub.3                                                                         OCH.sub.3                                                                          OCH.sub.3                                             Q-7 (R.sub.1 = SCH.sub.3)                                                                   5-CF.sub.3                                                                         CH.sub.3                                                                           OCH.sub.3                                             Q-7 (R.sub.1 = SCH.sub.3)                                                                   5-OCH.sub.3                                                                        CH.sub.3                                                                           OCH.sub.3                                             Q-7 (R.sub.1 = SCH.sub.3)                                                                   6-OCF.sub.2 H                                                                      CH.sub.3                                                                           OCH.sub.3                                             Q-7 (R.sub.1 = SCH.sub.3)                                                                   6-SCF.sub.2 H                                                                      OCH.sub.3                                                                          OCH.sub.3                                             Q-1           H    CH.sub.3                                                                           OC.sub.2 H.sub.5                                      Q-1           H    OC.sub.2 H.sub.5                                                                   NHCH.sub.3                                            Q-8           H    OCH.sub.3                                                                          N(OCH.sub.3)CH.sub.3                                  Q-9           H    CH.sub.3                                                                           N(OCH.sub.3)CH.sub.3                                  Q-1           1    OCF.sub.2 H                                                                        N(OCH.sub.3)CH.sub.3                                  Q-4           H    OCH.sub.3                                                                          N(CH.sub.3).sub.2                                     Q-1           H    OCH.sub.3                                                                          C.sub.2 H.sub.5                                       Q-16          H    OCH.sub.3                                                                          SCH.sub.3                                             Q-17          H    OCH.sub.3                                                                          OCH.sub.2 CHCH.sub.2                                  Q-1           H    CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                   Q-1           H    OCH.sub.3                                                                          OCF.sub.2 H                                           Q-1           H    OCH.sub.3                                                                          OCH.sub.2 CF.sub.3                                    Q-8           H    CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                    Q-16          H    OCH.sub.3                                                                          CH(CH.sub.3)(OCH.sub.3).sub.2                         Q-2           H    CH.sub.3                                                                            ##STR33##                                            Q-1           H    OCH.sub.3                                                                           ##STR34##                                            Q-7 (R.sub.1 = SCH.sub.2 CHCH.sub.2)                                                        H    OCH.sub.3                                                                          OCH.sub.3                                             Q-7 (R.sub.1 = SCH.sub.2 CHCH.sub.2)                                                        H    CH.sub.3                                                                           OCH.sub.3                                             Q-28          H    CH.sub.3                                                                           CH.sub.3                                              Q-28          H    OCH.sub.3                                                                          CH.sub.3                                              Q-29          H    CH.sub.3                                                                           CH.sub.3                                              Q-29          H    OCH.sub.3                                                                          CH.sub.3                                              Q-30          H    CH.sub.3                                                                           CH.sub.3                                              Q-30          H    OCH.sub.3                                                                          CH.sub.3                                              Q-31          H    CH.sub.3                                                                           CH.sub.3                                              Q-31          H    OCH.sub.3                                                                          CH.sub.3                                              Q-32          H    CH.sub.3                                                                           CH.sub.3                                              Q-32          H    OCH.sub.3                                                                          CH.sub.3                                              Q-33          H    CH.sub.3                                                                           CH.sub.3                                              Q-33          H    OCH.sub.3                                                                          CH.sub.3                                              Q-7 (R.sub.1 = SH)                                                                          H    OCH.sub.3                                                                          CH.sub.3                                              Q-7 (R.sub.1 = SH)                                                                          H    OCH.sub.3                                                                          OCH.sub.3                                             __________________________________________________________________________

                  TABLE III                                                       ______________________________________                                         ##STR35##                                                                    Q           R        X.sub.1   Y.sub.1                                                                            m.p. °C.                           ______________________________________                                        Q-1         H        CH.sub.3  O                                              Q-1         H        OCH.sub.3 O                                              Q-2         H        CH.sub.3  O                                              Q-2         H        OCH.sub.3 O                                              Q-3         H        CH.sub.3  O                                              Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        CH.sub.3  O    184-187                                   Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        OCH.sub.3 O                                              Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        OC.sub.2 H.sub.5                                                                        O                                              Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        OCF.sub.2 H                                                                             O                                              Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        OCH.sub.3 CH.sub.2                                       Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        CH.sub.3  CH.sub.2                                       Q-8         H        CH.sub.3  O                                              Q-9         H        CH.sub. 3 O                                              Q-16        H        CH.sub.3  O                                              Q-21        H        CH.sub.3  O                                              Q-23        H        CH.sub.3  O                                              ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                         ##STR36##                                                                    Q            R         X.sub.1  m.p. °C.                               ______________________________________                                        Q-1          H         CH.sub.3                                               Q-2          H         CH.sub.3                                               Q-3          H         CH.sub.3                                               Q-7 (R.sub.1 = SCH.sub.3)                                                                  H         CH.sub.3                                               Q-7 (R.sub.1 = SCH.sub.3)                                                                  H         OCH.sub.3                                              Q-7 (R.sub.1 = SCH.sub.3)                                                                  H         OC.sub.2 H.sub.5                                       Q-7 (R.sub.1 = SCH.sub.3)                                                                  H         OCF.sub.2 H                                            Q-8          H         CH.sub.3                                               Q-9          H         CH.sub.3                                               Q-16         H         CH.sub.3                                               Q-21         H         CH.sub.3                                               Q-23         H         CH.sub.3                                               ______________________________________                                    

                  TABLE V                                                         ______________________________________                                         ##STR37##                                                                    Q           R        X.sub.1   Y.sub.2                                                                            m.p. °C.                           ______________________________________                                        Q-1         H        CH.sub.3  CH.sub.3                                       Q-2         H        CH.sub.3  CH.sub.3                                       Q-3         H        CH.sub.3  CH.sub.3                                       Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        CH.sub.3  CH.sub.3                                       Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        OCH.sub.3 CH.sub.3                                       Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        OC.sub.2 H.sub.5                                                                        CH.sub.3                                       Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        OCF.sub.2 H                                                                             CH.sub.3                                       Q-7 (R.sub.1 = SCH.sub.3)                                                                 H        CH.sub.3  H                                              Q-8         H        CH.sub.3  CH.sub.3                                       Q-9         H        CH.sub.3  CH.sub.3                                       Q-16        H        CH.sub.3  CH.sub.3                                       Q-21        H        CH.sub.3  CH.sub.3                                       Q-23        H        CH.sub.3  CH.sub.3                                       ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid inertdiluent(s). More specifically, they will contain these ingredients inthe following approximate proportions:

                  TABLE VI                                                        ______________________________________                                                    Active  Weight Percent*                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74     1-10                                        Oil Suspensions,                                                                             3-50     40-95     0-15                                        Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84     1-20                                        Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9  0-15                                        High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates;solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents" Chemical Publishing Co., Inc., New York, 1964,list surfactants and recommended uses. All formulations can containminor amounts of additives to residue foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 9 Wettable Powder

    ______________________________________                                        N-[(4.6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          80%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            sodium alkylnaphthalenesulfonate                                                                            2%                                              sodium ligninsulfonate        2%                                              synthetic amorphous silica    3%                                              kaolinite                    13%                                              ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, re-blended, and packaged.

EXAMPLE 10 Wettable Powder

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          50%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            sodium alkylnaphthalenesulfonate                                                                            2%                                              low viscosity methyl cellulose                                                                              2%                                              diatomaceous earth           46%                                              ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 11 Granule

    ______________________________________                                        Wettable Powder of Example 11                                                                            5%                                                 attapulgite granules      95%                                                 (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing 25% solids is sprayed on thesurface of attapulgite granules while tumbling in a double-cone blender.The granules are dried and packaged.

EXAMPLE 12 Extruded Pellet

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          25%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            anhydrous sodium sulfate     10%                                              crude calcium ligninsulfonate                                                                               5%                                              sodium alkylnaphthalenesulfonate                                                                            1%                                              calcium/magnesium bentonite  59%                                              ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S. Ser. No. 20 sieve (0.84 mm openings). The granules held on a U.S.Ser. No. 40 sieve (0.42 mm openings) may be packaged for use and thefines recycled.

EXAMPLE 13 Oil Suspension

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          25%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            polyoxyethylene sorbitol hexaoleate                                                                         5%                                              highly aliphatic hydrocarbon oil                                                                           70%                                              ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 14 Wettable Powder

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          20%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            sodium alkylnaphthalenesulfonate                                                                            4%                                              sodium ligninsulfonate        4%                                              low viscosity methyl cellulose                                                                              3%                                              attapulgite                  69%                                              ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isre-blended and sifted through a U.S. Ser. No. 50 sieve (0.3 mm opening)and packaged.

EXAMPLE 15 Low Strength Granule

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                           1%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            N,N-dimethylformamide         9%                                              attapulgite granules         90%                                              (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 16 Aqueous Suspension

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                         40%                                               [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            polyacrylic acid thickener  0.3%                                              dodecylphenol polyethylene glycol ether                                                                   0.5%                                              disodium phosphate          1%                                                monosodium phosphate        0.5%                                              polyvinyl alcohol           1.0%                                              water                       56.7%                                             ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 17 Solution

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                           5%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide. sodium salt                                               water                        95%                                              ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 18 Low Strength Granule

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          0.1%                                             [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            attapulgite granules        99.9%                                             (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double-cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 19 Granule

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          80%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            wetting agent                 1%                                              crude ligninsulfonate salt (containing                                                                     10%                                              5-20% of the natural sugars)                                                  attapulgite clay              9%                                              ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 20 High Strength Concentrate

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                         99%                                               [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            silica aerogel              0.5%                                              synthetic amorphous silica  0.5%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S. Ser. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 21 Wettable Powder

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                         90%                                               [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            dioctyl sodium sulfosuccinate                                                                             0.1%                                              synthetic fine silica       9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 22 Wettable Powder

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          40%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            sodium ligninsulfonate       20%                                              montmorillonite clay         40%                                              ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 23 Oil Suspension

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          35%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            blend of polyalcohol carboxylic                                                                             6%                                              esters and oil soluble petroleum                                              sulfonates                                                                    xylene                       59%                                              ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 24 Dust

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          10%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            attapulgite                  10%                                              Pyrophyllite                 80%                                              ______________________________________                                    

The active ingredient is blended with attapulgite and then passedthrough a hammer-mill to produce particles substantially all below 200microns. The ground concentrate is then blended with powderedpyrophyllite until homogeneous.

EXAMPLE 25 Emulsifiable Concentrate

    ______________________________________                                        N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2-                                                          20%                                              [5-(methylthio)-1,3,4-oxadiazol-2-yl]benzene-                                 methanesulfonamide                                                            chlorobenzene                74%                                              sorbitan monostearate and polyoxyethylene                                                                   6%                                              condensates thereof                                                           ______________________________________                                    

The ingredients are combined and stirred to produce a solution which canbe emulsified in water for application.

Utility

Test results indicate that the compounds of the present invention arehighly active preemergent or postemergent herbicides or plant growthregulants. Many of them have utility for broad-spectrum pre- and/orpostemergence weed control in areas where complete control of allvegetation is desired, such as around fuel storage tanks, ammunitiondepots, industrial storage areas, parking lots, drive-in theaters,around billboards, highway and railroad structures. Alternatively, thesubject compounds are useful to modify plant growth.

The rates of application for the compounds of the invention aredetermined by a number of factors, including their use as plant growthmodifiers or as herbicides, the crop species involved, the types ofweeds to be controlled, weather, and climate, formulations selected,mode of application, amount of foilage present, etc. In general terms,the subject compounds should be applied at levels of around 0.05 to 10kg/ha, the lower rates being suggested for use on lighter soils and/orthose having a low organic matter content, for plant growth modificationor for situations where only short-term persistence is required.

The compounds of the invention may be used in combination with any othercommerical herbicide: examples of which are those of the triazine,triazole, uracil, urea, amide, diphenylether, carbamate and bipyridyliumtypes. The compounds may also be used in combination with merfluidide.

The herbicidal properties of the subject compounds were dissolved in anumber of greenhouse tests. The test procedures and results follow.

Test A

Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloacrusqualli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia),morningglory (Ipomoea spp.), cocklebur (Xanthium pensylvanicum),velvetleaf (Abutilon theophrasti), cheatgrass (Bromus secalinus),sorghum, corn, soybean, cotton, sugar beet, rice, wheat and purplenutsedge (Cyperus rotundus) tubers were planted and treated preemergencewith the test chemicals dissolved in a non-phytotoxic solvent. At thesame time, these crop and weed species were treated with a soil/foilageapplication. At the time of treatment, the plants ranged in height from2 to 18 cm. Treated plants and controls were maintained in a greenhousefor sixteen days, after which all species were compared to controls andvisually rated for response to treatment. The ratings, summarized inTable A, are based on a numerical scale extending from 0=no injury, to10=complete kill. The accompanying the descriptive symbols have thefollowing meanings:

C=chlorosis/necrosis;

B=burn;

D=defoliation;

E=emergence inhibition;

G=growth retardation;

H=formative effects;

U=unusual pigmentation;

X=axillary stimulation;

S=albinism; and

6Y=abscised buds or flowers. ##STR38##

                                      TABLE A                                     __________________________________________________________________________                Cmpd. 1                                                                            Cmpd. 2                                                                            Cmpd. 3                                                                            Cmpd. 4                                                                             Cmpd. 5                                                                            Cmpd. 6                                 Rate kg/ha  .05  .05  .05  .4  .05                                                                             .4   .4                                      __________________________________________________________________________    POST-EMERGENCE                                                                Morningglory                                                                              5C,9G                                                                              2C,6H                                                                              4C,9G                                                                              3C,7H                                                                             2H                                                                              3C,9H                                                                              3C,9G                                   Cocklebur   5G   1C   2C   2C,2H                                                                             0 3C,9G                                                                              2G                                      Sicklepod   2C   2C   4C,4H                                                   Velvetleaf                 3C,8H                                                                             5G                                                                              2C,5G                                                                              3C,7G                                   Nutsedge    2C,8G                                                                              2C,7G                                                                              8G   0   0 3G   0                                       Crabgrass   0    0    4G   0   0 0    0                                       Barnyardgrass                                                                             3G   0    4H   0   0 0    0                                       Cheatgrass  --   --   --   0   0 2C   2C,4G                                   Wild Oats   0    0    0    0   0 0    4C,6G                                   Wheat       0    0    0    0   0 2C,7G                                                                              3C,7H                                   Corn        0    0    2C,5H                                                                              0   0 2C,7G                                                                              3C,7H                                   Soybean     2H,3G                                                                              2C,5H                                                                              3C,8H                                                                              0   0 1H   3C,6H                                   Rice        3G   0    3G   0   0 3G   4G                                      Sorghum     3G   0    2C,5G                                                                              0   0 3C,7H                                                                              3C,8H                                   Sugar beet  3G   2C   9C   3C,6H                                                                             0 3C,8H                                                                              3C,8H                                   Cotton      5C,9G                                                                              2C,5G                                                                              4C,9G                                                                              1C  0 3C,9H                                                                              3C,7G                                   PRE-EMERGENCE                                                                 Morningglory                                                                              9G   2H   9G   2C  0 2C,8G                                                                              8G                                      Cocklebur   3G   0    --   2C  2G                                                                              1C   0                                       Sicklepod   0    0    2C                                                      Velvetleaf                 2C,5G                                                                             0 2G   0                                       Nutsedge    0    0    7G   0   0 0    0                                       Barnyardgrass                                                                             0    0    2C   1C  0 0    0                                       Cheatgrass  --   --   --   2G  0 5G   3G                                      Wild Oats   0    0    0    0   0 1C   2G                                      Wheat       0    0    0    0   0 4G   5G                                      Corn        2C,3G                                                                              0    2G   1C  0 2C,4G                                                                              2G                                      Soybean     2H   0    2C,2H                                                                              1C  0 0    0                                       Rice        2C   0    3C,5G                                                                              1C  0 2C,3G                                                                              0                                       Sorghum     2C,6H                                                                              0    2C,6H                                                                              2C  0 3C,8G                                                                              2C,8G                                   Sugar beet  3C,7G                                                                              2H   3C,5G                                                                              5G  0 3C,8H                                                                              2G                                      Cotton      3C,6G                                                                              0    5G   0   0 0    0                                       __________________________________________________________________________

What is claimed is:
 1. The compound methyl2-[(aminosulfonyl)methyl]-benzoate.